WO2015123162A1 - Sulfosuccinates d'alkoxylate de tristyrylphénol - Google Patents

Sulfosuccinates d'alkoxylate de tristyrylphénol Download PDF

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Publication number
WO2015123162A1
WO2015123162A1 PCT/US2015/015115 US2015015115W WO2015123162A1 WO 2015123162 A1 WO2015123162 A1 WO 2015123162A1 US 2015015115 W US2015015115 W US 2015015115W WO 2015123162 A1 WO2015123162 A1 WO 2015123162A1
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Prior art keywords
emulsion
och
hydrogen
surfactant
latex
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PCT/US2015/015115
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English (en)
Inventor
Gary Luebke
Keith RESCHAK
Renee Luka
Jarrod KALTENBACH
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Stepan Company
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Publication date
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Priority to MX2016010143A priority Critical patent/MX2016010143A/es
Priority to BR112016018484-0A priority patent/BR112016018484B1/pt
Priority to CN201580008582.0A priority patent/CN105980465B/zh
Priority to EP15748591.3A priority patent/EP3105285B1/fr
Publication of WO2015123162A1 publication Critical patent/WO2015123162A1/fr
Priority to US15/228,783 priority patent/US10040964B2/en
Priority to US16/026,564 priority patent/US20180312712A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/45—Anti-settling agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/36—Polymerisation in solid state
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/027—Dispersing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

  • Emulsion polymerization can be used to produce polymer dispersions in water, more commonly referred to as latexes.
  • Polymer latexes are used in many applications such as adhesives, carpet backing, caulks, coatings, elastomers, paints and packaging.
  • Latexes are typically stable colloidal suspensions of polymer particles in water. When the particles are sufficiently small they can be individually stabilized through the use of surfactants and kept dispersed through Brownian motion.
  • the emulsion polymerization process can be performed in an aqueous medium in the presence of a surfactant or combination of surfactants.
  • Surfactants play a role in both the formation of emulsion polymer latexes and in stabilizing the final polymer dispersion.
  • Water soluble free radical initiators such as ammonium, sodium, or potassium persulfate can be used to rapidly produce high molecular weight polymers at relatively high solids content and low viscosity.
  • the process requires the emulsification of the monomers in the aqueous phase through the use of surfactants.
  • ingredients used in the emulsion polymerization process may include buffers and chain transfer agents and minor amounts of polymerizable acids such as acrylic acid, methacrylic acid, or itaconic acid. Since the surfactant cannot be easily removed from the final latex, normally remaining imbedded in the polymer matrix, the quantity and type of surfactant used can determine many of the characteristics of the latex and performance characteristics in a final application.
  • the surfactants remaining in a latex can have deleterious effects in the final application.
  • water sensitivity and poor adhesion can be caused by the migration of surfactants within a dried polymer matrix.
  • Surfactants can migrate to form domains within the polymer matrix as well as migrate to surfaces and interfaces.
  • Surfactant domains at the surface can lead to the formation of micro-voids that can leave the polymer film vulnerable to the penetration of moisture leading to water sensitivity and degradation of polymer film strength.
  • the presence of surfactant at the polymer-substrate interface can lead to reductions in adhesive strength.
  • the disclosure relates to surfactant-containing compositions for use in synthesis of emulsion polymer latexes.
  • Such latexes can be used in coatings, paints, and adhesives, among other applications.
  • the surfactant compositions can be used in low glass transition temperature emulsion polymer latex compositions, such as those used to formulate low VOC latex paints, and high glass transition temperature emulsion polymer latex compositions, such as those used in coating compositions and other compositions employing surfactants.
  • the disclosure provides emulsions comprising:
  • G and G 1 are -SO 3 M and the other is hydrogen, wherein M is hydrogen or a metal cation (e.g., Na + );
  • R is -OH, -R 1 , or -R 3 ; wherein each R 1 is independently -L-R 2 , wherein
  • each L is independently -(OCH(CH 3 )CH2)n-(OCH 2 CH2)m-*
  • n and m are each between 0 and 1 00, provided that at least one of m and n is greater than or equal to 1 ;
  • R 3 is -L-OR 4 or d-30 alkoxy, wherein -OR 4 is attached to L at the * and R 4 is hydrogen or Ci -4 alkyl.
  • the present disclosure provides processes for preparing an emulsion polymer latex comprising, polymerizing a monomer emulsion in the presence of an initiator to form an emulsion polymer latex, wherein the monomer emulsion comprises:
  • the present disclosure provides the emulsion polymer latexes prepared according to the preceding aspect.
  • the present disclosure provides latex paints comprising polymeric latex particles that comprise a surfactant of one or more compounds defined by formula (I), above.
  • the present disclosure provides pressure-sensitive adhesives comprising polymeric latex particles that comprise a surfactant of one or more compounds defined by formula (I), above.
  • At least one aspect of the presently described technology provides latex paint formulations having reduced coagulum and/or improved water resistance, blister resistance, and leveling characteristics.
  • At least one further aspect of the presently described technology provides pressure-sensitive adhesive latexes having improved water resistance characteristics.
  • Figure 1 shows a comparison between a latex film made from a latex comprising a surfactant of the present technology, and a latex film made from a latex comprising a surfactant of the prior art.
  • the presently described technology is distinct from polymerizable surfactants such as surfmers in that the surfactants are not covalently or ionically bound to a polymer.
  • the surfactants described in this disclosure do not rely on a contained (i.e., covalently or ionically bound) reactive moiety.
  • the surfactants described below present fewer difficulties in handling, and can be less expensive than polymerizable surfactants.
  • latexes made using the surfactants described herein may be easier to formulate since the surface activity of the included surfactants is attenuated and less likely to interfere/compete with surfactants added for other purposes, such as dispersion aids, rheology modifiers, flow and leveling agents, anti-foaming agents, freeze-thaw and calcium ion stabilizers, and other additives with surface activity.
  • emulsion polymer latexes can be prepared by polymerizing a monomer emulsion in the presence of an initiator to form the emulsion polymer latex.
  • the monomer emulsion can comprise (i) water, (ii) at least one radical-polymerizable monomer; and (iii) a surfactant.
  • the surfactant is one or more compounds according to formula (I),
  • G and G 1 are -S0 3 M and the other is hydrogen, wherein M is hydrogen or a metal cation (e.g., Na);
  • R is -OH, -R 1 , or -R 3 ; wherein each R 1 is independently -L-R 2 , wherein
  • each L is independently -(OCH(CH3)CH2)n-(OCH 2 CH2)m- or -(OCH 2 CH2)m-(OCH(CH3)CH2)n-*, wherein R 2 is attached to L at the *; and n and m are each between 0 and 100, provided that at least one of m and n is greater than or equal to 1 ; and R 3 is -L-OR 4 or d-30 alkoxy, wherein -OR 4 is attached to L at the * and R 4 is hydrogen or Ci -4 alkyl.
  • One of the ester substituents could be C1 to C30 alcohol or C1 to C30 alkoxylate (EO, PO or EO+PO).
  • the surfactant of formula (I) is one or more compounds according to formula (II),
  • the surfactant of formula (I) is one or more compounds according to formula (III),
  • the surfactant of formula (I) is one or more compounds according to formula (IVa) or (IVb),
  • the surfactants of formula (I) can be prepared by reacting a monostyrylphenol, distyrylphenol, or tristyrylphenol alkoxylate, or a mixture thereof (i.e., a compound of the formula R 2 -L-H, as defined above, wherein q is 1 , 2, or 3, or mixture thereof) with maleic anhydride at a temperature suitable to open the anhydride ring
  • a surfactant of formula (I) can be prepared by reacting a monostyrylphenol, distyrylphenol, or tristyrylphenol alkoxylate, or a mixture thereof (i.e., a compound of the formula R 2 -L-H, as defined above) with maleic anhydride at a temperature suitable to open the ring and split off 1 mole of water (e.g., at 1 80 °C) to
  • the half-ester intermediate can be reacted with an alcohol of the formula R 3 -H at a temperature suitable to split off 1 mole of water (e.g., at 1 80 °C) to form the mixed diester
  • the order of preceding reactions could be reversed such that maleic anhydride is first reacted with R 3 -H, then the half ester reacted with R 2 -L-H.
  • the half-ester, diester, or mixed diester intermediate can be reacted with sodium bisulfite to form the surfactant according to formula (I).
  • M is an alkali metal cation or alkali earth metal cation. In another embodiment of any of the surfactants of formulae (I) - (IV), M is Li + , Na + , or K + . In another embodiment of any of the surfactants of formulae (I) - (IV), M is Na + .
  • R 1 is - (OCH(CH 3 )CH 2 ) n -(OCH 2 CH 2 ) m -R 2 .
  • R 1 is -(OCH 2 CH2)m-(OCH(CH3)CH 2 )n-R 2
  • R 1 is -(OCH 2 CH 2 ) m -R 2 .
  • R 1 is -(OCH(CH 3 )CH 2 ) n -R 2 .
  • R 2 is
  • n and m when present, can be each independently from 1 to 50.
  • m when present, is from 1 to 30, or is from 1 to 25, or is from 1 to 20, or is from 1 to 15, or is from 10 to 30, or is from 10 to 25, or is from 10 to 20.
  • n when present, is from 1 to 20, or is from 1 to 10, or is from 1 to 5.
  • surfactants described above include those defined by:
  • R is -OH, G is -SO 3 Na, G 1 is hydrogen, m is 16, n is 0, and q is a mixture of 1 , 2, and 3;
  • R is -OH, G is -SO 3 Na, G 1 is hydrogen, m is 4, n is 0, and q is a mixture of 1 , 2, and 3;
  • R is -OH, G is -SO 3 Na, G 1 is hydrogen, m is 16, n is 1 .5, and q is a mixture of 1 , 2, and 3;
  • R is R 1 , G is -SO 3 Na, G 1 is hydrogen, m is 8, n is 0, and q is a mixture of 1 , 2, and 3;
  • R is -OH
  • G is -SO3Na
  • G 1 is hydrogen
  • m is 8
  • n is 0, and q is a mixture of 1 , 2, and 3;
  • R is -OH, G is -SO3Na, G 1 is hydrogen, m is 7, n is 8, and q is a mixture of 1 , 2, and 3;
  • salts thereof e.g., sodium salts thereof.
  • the surfactant according to any of the preceding is a salt.
  • Salt as used herein means a compound formed between a cation and an anion of the surfactant of formula (I), (II), (III), or (IV).
  • the anion of the surfactant of formulae (I), (II), (III), or (IV) can be a monoanion or a dianion.
  • Suitable salts include, but are not limited to, organic salts (e.g., ammonium salts), Group (I) cationic salts (e.g., lithium, sodium, or potassium salts), and Group (I I) cationic salts (e.g., magnesium or calcium salts).
  • the surfactant according to any of the preceding embodiments is a sodium salt (e.g., a monosodium or disodium salt).
  • the surfactant according to any of the preceding embodiments is an ammonium salt (e.g., a mono-ammonium or di-ammonium salt).
  • the surfactant according to any of the preceding embodiments is a tetra(Ci -4 alkyl)ammonium salt (e.g., tetra(n-butyl)ammonium (e.g., a mono- tetra(n- butyl)ammonium or di- tetra(n-butyl)ammonium salt).
  • Alkyl as used herein means a monovalent, straight or branched, or cyclic saturated hydrocarbon chain having one to thirty carbon atoms unless defined otherwise (e.g., C-i -4 alkyl contains 1 - 4 carbon atoms).
  • alkyl groups include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, n-pentyl, neo- pentyl, n-hexyl, 2-ethylhexyl, cyclochexyl, n-octyl, n-decyl, and the like.
  • alkoxy as used herein means an alkyl group, as defined here, connected to a parent chemical moiety through an oxygen atom.
  • Representative examples of “alkoxy” groups include methoxy, ethoxy, isopropoxy, octyloxy, decyloxy, dodecyloxy, and the like.
  • any ethylenically unsaturated monomer that is capable of undergoing radical-initiated polymerization may be utilized as the at least one radical polymerizable monomer to prepare an emulsion polymer latex according to the preceding description.
  • Radical-polymerizable monomers that may be polymerized or co- polymerized in the presence of a radical initiator are known to the art and are described below in a representative manner.
  • radical-polymerizable monomers examples include (a) acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, aconitic acid, citraconic acid, and esters and/or amides thereof, (b) vinyl and allyl monomers, (c) ethylene and C 4 . 8 conjugated dienes, and mixtures of (a)-(c).
  • radical-polymerizable monomers (a) include: acrylic esters and methacrylic esters such as C-1 -12 (e.g., C-i -4 ) alkyl acrylates and methacrylates, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 3,3-dimethylbutyl acrylate, 3,3-dimethyl butyl methacrylate, lauryl acrylate, lauryl methacrylate, lauryl acryl
  • vinyl ketones include methylvinyl ketone, ethylvinyl ketone and isobutylvinyl ketone; vinyl amines and amides such as N- vinylpyrrolidone (NVP), N-acetyl vinylamine, and N-vinylcarbazole (NVC); styrene- derivatives such as styrene, a-methyl styrene, vinyl toluene, 4-(tert-butyl)styrene, 4- chloromethylstyrene, 4-methylstyrene, 4-nitrostyrene, 4-tert-butoxystyrene, 4- vinylbenzoic acid, and chloromethylstyrene; and allyl derivatives of the preceding.
  • NRP N- vinylpyrrolidone
  • NVC N-vinylcarbazole
  • styrene- derivatives such as styrene, a-methyl styrene
  • radical-polymerizable monomers (c) include ethylene, and C 4 . 8 conjugated dienes, such as 1 ,3-butadiene, isoprene and chloroprene.
  • the at least one radical-polymerizable monomer comprises acrylic acid, methacrylic acid, or a mixture thereof (e.g., greater than 0 and less than or equal to about 2 wt.% based on all monomers) and one or more additional monomers selected from the group consisting of vinyl monomers (e.g., styrene), acrylate monomers (e.g Ci -4 alkyl acrylates), methacrylate monomers (e.g., C-i -4 alkyl methacrylates), and mixtures thereof.
  • vinyl monomers e.g., styrene
  • acrylate monomers e.g Ci -4 alkyl acrylates
  • methacrylate monomers e.g., C-i -4 alkyl methacrylates
  • the at least one radical-polymerizable monomer comprises methacrylic acid (e.g., greater than 0 and less than or equal to about 2 wt.% based on all monomers), methyl methacrylate, and n-butyl acrylate.
  • the at least one radical-polymerizable monomer comprises acrylic acid (e.g., greater than 0 and less than or equal to about 2 wt.% based on all monomers), methyl acrylate, and n-butyl acrylate.
  • the at least one radical-polymerizable monomer comprises acrylic acid (e.g., greater than 0 and less than or equal to about 2 wt.% based on all monomers), and methyl methacrylate, hydroxyethyl methacrylate phosphate, hydroxyethyl acrylate phosphate, hydroxypropyl methacrylate phosphate, hydroxypropyl acrylate phosphate, or a mixture thereof.
  • the monomer emulsion may contain additional, optional components that are compatible with the radical polymerization process.
  • suitable additional components include chain-transfer agents and buffers.
  • chain-transfer agents include thiocarbonylthio compounds such as dithioesters, dithiocarbamates, trithiocarbonates, and xanthate, such as 2-cyano-2-propyl benzodithioate , 4-cyano-4- [(dodecylsulfanylthiocarbonyl) sulfanyl]pentanoic acid, cyanomethyl methyl(phenyl) carbamodithioate, 4-cyano-4-(phenylcarbonothioylthio) pentanoic acid, 2-cyano-2-propyl dodecyl trithiocarbonate, 2-(dodecylthiocarbonothioylthio)-2-methylpropionic acid, and cyanomethyl dodecyl trithiocarbonate.
  • the surfactant as described above can be used in the monomer emulsion at about 0.1 wt% to about 5 wt% based on weight of all monomers to be polymerized with a conventional free radical emulsion polymer system to produce latexes with good polymerization kinetics, particle size distributions as well as low coagulum levels.
  • the monomer emulsion comprises about 0.1 wt% to 3 wt%, about 1 wt% to 3 wt%, or about 0.1 wt% to 2 wt%, or about 1 wt% to 2 wt% of the surfactant.
  • the surfactant described above can provide, after polymerization, an emulsion polymer latex comprising polymer particles having a mean diameter of between about 50 nm and about 300 nm.
  • the polymeric latex particles can have a mean diameter of less than about 200 nm, or less than about 175 nm, or less than about 150 nm.
  • the polymeric latex particles have a mean diameter of greater than about 75 nm, or greater than about 100 nm.
  • polymer latexes having a mean polymeric latex particle diameter of between about 50 nm and about 300 nm can be prepared using less surfactant on a molar basis with respect to standard surfactants, such as sodium dodecylbenzene sulfonate (SDS). This result is in direct contrast with the expectation of one skilled in the art. Generally, it would be expected that a higher molar amount of a surfactant would be required to decrease the average particle size of a resulting latex.
  • standard surfactants such as sodium dodecylbenzene sulfonate (SDS).
  • a latex can be prepared that has a smaller average particle diameter than a latex prepared under the same conditions, but using a standard surfactant, such as SDS.
  • a standard surfactant such as SDS.
  • the same wt% of the surfactant of formula (I) represents a lower molar amount of surfactant than if the same wt% of a standard surfactant were used.
  • the polymerization processes to prepare the emulsion polymer latex can be carried out at from about 20 °C to about 120 °C; alternatively, between about 50 °C and about 1 10 °C.
  • the polymerization temperature selected will vary, depending on the reactivity and concentration of the polymerization initiator and monomer(s) being used.
  • Batch polymerization times may vary depending on the method of polymerization and the monomer(s) being polymerized. Such times may vary from about 10 minutes to about 10 hours.
  • Suitable initiators include those known to one skilled in the art for preparing emulsion polymers, such as peroxides including conventional benzoyl peroxide (BPO), azodiisobutyronitrile (AIBN), 4,4'-azobis(4-cyanovaleric acid) (ACVA), sodium persulfate, ammonium persulfate, potassium persulfate, and hydrogen peroxide.
  • BPO benzoyl peroxide
  • AIBN azodiisobutyronitrile
  • ACVA 4,4'-azobis(4-cyanovaleric acid)
  • the amount of initiator can be from about 0.1 to about 8 percent by weight of the entire monomer emulsion.
  • the amount of initiator can be from about 2 to about 6 percent by weight of the entire monomer emulsion.
  • a polymer latex having an average particle size of less than 125 nm and greater than about 75 nm, for example, about 100 nm can be prepared using a surfactant of formula (I), (II), (III), or (IV) that contains essentially no coalgulate.
  • the latexes prepared using a surfactant of formula (I), (II), (III), or (IV) show increased water resistance with respect to latexes prepared using SDS as a surfactant.
  • the latexes prepared using a surfactant of formula (I), (II), (III), or (IV) show increased water resistance with respect to latexes prepared using TSP-16 sulfate as a surfactant.
  • TSP-16 sulfate is a surfactant of the formula
  • the latexes prepared using a surfactant of formula (I), (II), (III), or (IV) have a delta L * value of less than 10, or less than 9 or less than 8 or less than 7 or less than 6 or less than 5 or less than 4, as measured according to the method described in Example 16.
  • the latexes prepared using a surfactant of formula (I), (II), (III), or (IV) have an opacity of less than 5, or less than 2, or less than 1 as measured according to the method described in Example 27.
  • the latexes prepared using a surfactant of formula (I), (II), (III), or (IV) have an opacity of between 0 and 5, or between 0 and 2, or between 0 and 1 , as measured according to the method described in Example 27.
  • the preceding emulsion polymer latexes can be, for example, acrylic, styrene-acrylic, and vinyl-acrylic latexes that are prepared to have a glass-transition temperature suitable for a desired application.
  • higher glass transition temperature emulsion polymer latexes can be used in coating and paint applications and can improve or modify, for example, block resistance, adhesion, gloss, pigment dispersion, and blister resistance in paints, as well as water resistance in paints and coatings.
  • Lower glass transition temperature emulsion polymer latexes can be used in adhesive type applications and can improve or modify, for example adhesion and water resistance.
  • the emulsion polymer latex compositions can include a variety of additional components, depending on the intended use of the composition.
  • the composition may also comprise one or more pigments, secondary surfactants, coalescing agents, thickening agents, biocides, and combinations thereof when utilized for a latex paint composition.
  • suitable pigments include titanium dioxide (TI-PURE® R-746, E.I. du Pont de Nemours and Company, Wilmington, Delaware), calcium carbonate, aluminum silicate, magnesium silicate, carbon black and iron oxide.
  • suitable coalescing agents or solvents include, but are not limited to, TEXANOLTM (an ester alcohol commercially available from Eastman Chemical Company, Kingsport, Tennessee), and glycol ethers, such as propylene glycol.
  • suitable thickening agents include ACRYSOLTM SCT-275 (an associative type thickener commercially available from Rohm and Haas Company (Philadelphia, PA)), cellulosic thickeners such as hydroxylated cellulose and alkali soluble-type thickeners.
  • suitable biocides include ACTICIDE® MBS biocide (a 1 :1 (by wt.) of 1 ,2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, Thor Specialties, Inc., Shelton, Connecticut).
  • Suitable secondary surfactants for example, surfactants added to the final latex composition, but not used in preparing the latex, include MAKON ® TD-9 (Stepan Co., Northfield, Illinois). Examples also include AEROSOL OT-75, which is not required to prepare the pressure sensitive adhesive latex, but can be used as a post-additive to enhance wetting.
  • the glass transition temperatures (T g ) of emulsion polymer latexes used to formulate latex paints can be about -20 °C to about 80 °C, alternatively greater than about 5 °C; for example, the T g can be between about 15 °C and about 80 °C. In some embodiments, if the T g of the paint coating is below about 15 °C, blocking can occur. On the other hand, if the T g is above about 80 °C, the coating may be too brittle and susceptible to cracking. T g may be measured using differential scanning calorimetry (DSC) according to methods familiar to those skilled in the art.
  • DSC differential scanning calorimetry
  • the latex paints prepared using a latex that was prepared with surfactant of formula (I), (II), (III), or (IV) show good leveling characteristics as measured according to Example 15. In certain other embodiments, the latex paints prepared using a latex that was prepared with surfactant of formula (I), (II), (III), or (IV) show blister resistance as measured according to Example 15. In other embodiments, the latex paints prepared using a latex that was prepared with surfactant of formula (I), (II), (III), or (IV) show good leveling characteristics and blister resistance, each as measured according to Example 15. [0053] Alternatively, the expected T g of a polymer can also be based on its composition.
  • coating applications and/or compositions containing polymers that can exhibit a T g between about 5 °C and about 80 °C exhibit minimum film-forming temperature (MFFT) (based upon the latex polymer, pigment, coalescing aides, etc.) of about 4 °C or greater.
  • the MFFT is related to the T g of the polymer, but is also affected by the other components of the formulation (e.g., coalescing aides, pigments, etc.).
  • the T g or MFFT of the present technology can be evaluated depending upon the polymer latexes or the paints or other coating compositions of the present technology.
  • the emulsion polymer latexes described above can be used in applications that are affected by surfactant migration, for example, in the area of clear pressure-sensitive adhesives.
  • Pressure-sensitive adhesive systems are adhesives that are aggressively and permanently tacky at room temperature in the dry form. There is no curing agent required in such systems, and they adhere without the need of more than finger or hand pressure. Further, pressure-sensitive adhesive systems require no activation by water, solvent, or heat.
  • the glass transition temperatures (T g ) of pressure sensitive adhesives with which the present technology is typically used depend somewhat on the particular application, but are generally about 30 to about 70 °C below the intended use temperature, or less than about (-)15 °C and preferably between about (-)60°C and about (-)40 °C.
  • the T g of individual components of pressure sensitive adhesives can range between about (-)90°C to about 365 °C. It will be appreciated by those skilled in the art that the T g of the polymer latexes of the present technology will vary depending upon the end use or end application desired.
  • Tristyrylphenol poly(ethylene oxide)- and tristyrylphenol polypropylene oxide- block-ethylene oxide)-sulfosuccinates were synthesized.
  • Various TSP alkoxylate sulfosuccinate derivatives were then evaluated as primary emulsion polymer surfactants to produce stable latexes with good particle size distributions and fast polymerization kinetics.
  • the resulting latexes were formulated into latex paint formulations which exhibited good alkaline stability, and good overall paint properties with improvement in blister resistance, wet film leveling, and dry paint film water resistance as compared to a latex made with a conventional anionic surfactant (e.g. POLYSTEP® A-15, infra).
  • PSA type latexes were created using the aforementioned surfactants which exhibited improvements in latex film water resistance as compared to a latex made with a conventional anionic surfactant (e.g. POLYSTEP TSP-16S).
  • the reactor was cooled to 58 °C and 2.4 g sodium bicarbonate followed by 28 g water and 16 g ethanol, pH was adjusted from 4.0 to 6.8 with 21 .2 g 50 % sodium hydroxide along with an additional 50 g water and 41 g ethanol to reduce viscosity.
  • the reaction was maintained at 55 °C for 90 minutes at which time proton NMR indicated complete conversion to the sulfonate.
  • the pH was adjusted from 6.1 to 7.0 with 2.5 g 50 % sodium hydroxide. A total of about 200 g water and 80 g ethanol had been added to the reaction.
  • the reactor was fitted with a Dean-Stark tube and condenser and heated to 70 °C while pulling a vacuum of about 250 mm Hg to remove ethanol as collected in Dean-Stark. Water was periodically added to the reactor to replenish that lost in the ethanol removal process. After about two hours, the reaction content was transferred to a jar; it formed a white paste as it cooled with oven solids of 35.3 % and pH of 7.0
  • the reaction was heated to reflux of 67 °C for an hour followed by the attachment of a Dean- Stark tube for the removal of methanol over a period of about 30 minutes. Once the methanol was removed, the reaction was cooled resulting in the recovery of 199 g of TSP-8 sulfosuccinate diester with calculated solids of 80 %. The final product was a fluid amber hazy liquid.
  • the reactor was cooled to 60 °C, 32 g water and 14 g ethanol added followed by the addition of 7.3 g 50 % NaOH to pH 4.5. 12.2 g sodium bisulfate (0.12 mol) dissolved in 40 g water slowly added. The reaction mixture thickened as sodium bisulfite was added, 7 g additional ethanol and 90 g water were. pH was adjusted to 5.7 with 3.3 g 50 % NaOH along with an additional 50 g water and 41 g ethanol to reduce viscosity. The reactor was fitted with a Dean-Stark tube and condenser, heated to 70 °C while pulling a vacuum of about 250 mm Hg to remove ethanol collected in the Dean-Stark tube. Water was periodically added to the reactor to replenish that lost in the ethanol removal process. Transferred viscous material to a jar. Final oven solids of 44.4 % and pH of 5.9.
  • Example 7 Latex Synthesis Using Surfactant (3.0%) from Example 1
  • the ME was prepared by adding 58.0 g of the sulfosuccinate half-ester as described in example 1 in 107 g Dl water to which was added with vigorous agitation a monomer mixture of 260 g butyl acrylate, 230 g methyl methacrylate and 10 g methacrylic acid and stirred for 10 minutes. Within three minutes after the addition of the ME and ammonium persulfate initiator an exotherm to 85 °C was observed indicating polymerization of the monomers. Dynamic light scattering indicated the in-situ seed average particle size distribution to be 43 nm.
  • the ME was added by metering pump over a three hour period concurrent with the addition of a solution consisting of 2.7 g ammonium persulfate, 1 .5 g sodium bicarbonate dissolved in 75 g Dl water.
  • the reaction temperature was maintained at 83 °C.
  • the ME and initiator feed additions were complete.
  • the ME addition line was flushed with 50 g Dl water into the reactor. The reaction was maintained at 83 °C for an additional hour, and then cooled with blown air to room temperature.
  • the resulting latex was pH adjusted from 5.4 to 7.5 with 6.6 g of dilute ammonium hydroxide followed by the addition of 0.6 g ACTICIDE ® MBS biocide (1 :1 (by wt.) of 1 ,2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3- one, Thor Specialties, Inc., Shelton, Connecticut).
  • the latex was filtered through a 100 mesh screen, 0.06 g of coagulum was collected on the screen.
  • the reactor was clean- free of coagulum build-up.
  • the final average latex particle size was 175 nm.
  • Example 7 The same general procedure described in Example 7 was followed.
  • the ME was prepared by adding 58.8 g of the sulfosuccinate half-ester as described in example 2 in 107 g Dl water to which was added with vigorous agitation the monomer composition described in Example 5. 14.8 g of the ME was added to the 83 °C reaction vessel and allowed to polymerize to form an in-situ seed of 49 nm. After three hour addition of ME and initiator feeds followed by an one hour cook followed by cooling the resulting latex was pH adjusted from 5.4 to 7.5 with 6.4 g dilute ammonium hydroxide followed by the addition of 0.6 g ACTICIDE ® MBS biocide.
  • Example 9 Latex Synthesis Using Surfactant (3.0%) from Example 3
  • the resulting latex was pH adjusted from 5.3 to 7.0 with 1 1 .2 g dilute ammonium hydroxide followed by the addition of 0.6 g ACTICIDE ® MBS biocide.
  • the latex was filtered through a 100 mesh screen, 0.01 g of coagulum was collected on the screen. The reactor was clean- free of coagulum build-up.
  • the final average latex particle size was 120 nm.
  • Example 7 The same general procedure described in Example 7 was followed.
  • the ME was prepared by adding 19.7 g of POLYSTEP ® A-15 (Stepan Co., Northfield, Illinois), which is a sodium salt of linear dodecylbenzene sulfonate at 22.8 % solids to 135 g Dl water to which was added with vigorous agitation the monomer composition described in Example 5. 13.0 g of the ME was added to the 83 °C reaction vessel and allowed to polymerize to form an in-situ seed.
  • POLYSTEP ® A-15 Stepan Co., Northfield, Illinois
  • the resulting latex was pH adjusted from 5.3 to 7.2 with 5.0 g dilute ammonium hydroxide followed by the addition of 0.6 g ACTICIDE ® MBS biocide.
  • the latex was filtered through a 100 mesh screen, 0.03 g of coagulum was collected on the screen.
  • the reactor was clean-free of coagulum buildup.
  • the final average latex particle size was 188 nm.
  • the ME was prepared by adding 52.3 g of the sulfosuccinate half-ester as described in example 1 in 107 g Dl water to which was added with vigorous agitation a monomer mixture of 260 g butyl acrylate, 230 g methyl methacrylate and 10 g methacrylic acid and stirred for 10 minutes. Within three minutes after the addition of the ME and ammonium persulfate initiator an exotherm to 85 °C was observed indicating polymerization of the monomers. Dynamic light scattering indicated the in-situ seed average particle size distribution to be 48 nm.
  • the ME was added by metering pump over a three hour period concurrent with the addition of a solution consisting of 2.7 g ammonium persulfate, 1 .5 g sodium bicarbonate dissolved in 75 g Dl water.
  • the reaction temperature was maintained at 83 °C.
  • the ME and initiator feed additions were complete.
  • the ME addition line was flushed with 50 g Dl water into the reactor.
  • the reaction was maintained at 83 °C for an additional hour, and then cooled with blown air to room temperature.
  • 0.6 g ACTICIDE ® MBS biocide was added.
  • the latex was filtered through a 100 mesh screen, essentially coagulum free.
  • the reactor was clean- free of coagulum build-up.
  • the final average latex particle size was 1 15 nm.
  • the ME was prepared by adding 29.1 g of the sulfosuccinate half-ester as described in example 1 in 128 g Dl water to which was added with vigorous agitation a monomer mixture of 260 g butyl acrylate, 230 g methyl methacrylate and 10 g methacrylic acid and stirred for 10 minutes. Within three minutes after the addition of the ME and ammonium persulfate initiator an exotherm to 85 °C was observed indicating polymerization of the monomers. Dynamic light scattering indicated the in-situ seed average particle size distribution to be 56 nm.
  • the ME was added by metering pump over a three hour period concurrent with the addition of a solution consisting of 2.7 g ammonium persulfate, 1 .5 g sodium bicarbonate dissolved in 75 g Dl water.
  • the reaction temperature was maintained at 83 °C.
  • the ME and initiator feed additions were complete.
  • the ME addition line was flushed with 50 g Dl water into the reactor.
  • the reaction was maintained at 83 °C for an additional hour, and then cooled with blown air to room temperature.
  • 0.6 g ACTICIDE ® MBS biocide was added.
  • the latex was filtered through a 100 mesh screen, essentially coagulum free.
  • the reactor was clean- free of coagulum build-up.
  • the final average latex particle size was 204 nm.
  • the reaction vessel was heated to 83 °C and an in- situ latex seed was prepared by the addition of 43 g of monomer emulsion (ME) followed by a solution consisting of 1 .0 g ammonium persulfate, 0.5 g sodium bicarbonate dissolved in 20 g Dl water.
  • ME monomer emulsion
  • the ME was prepared by adding 48.3 g of POLYSTEP ® TSP-16S in 1 15 g Dl water to which was added with vigorous agitation a monomer mixture of 260 g butyl acrylate, 230 g methyl methacrylate and 10 g methacrylic acid and stirred for 10 minutes.
  • the reaction was maintained at 83 °C for an additional hour, and then cooled with blown air to room temperature.
  • 0.6 g ACTICIDE ® MBS biocide was added.
  • the latex was filtered through a 100 mesh screen the presence of large quantities of coagulum made filtration difficult.
  • the reactor and agitator blades contained significant build-up.
  • the final average latex particle size was 1 15 nm.
  • the reaction vessel was heated to 83 °C and an in-situ latex seed was prepared by the addition of 17.5 g of monomer emulsion (ME) followed by a solution consisting of 1 .0 g ammonium persulfate, 0.5 g sodium bicarbonate dissolved in 20 g Dl water.
  • ME monomer emulsion
  • the ME was prepared by adding 48.3 g of tristyrylphenol 16 mole ethoxylate sulfate (POLYSTEP ® TSP-16S) at 27.3 % solids in 1 15 g Dl water to which was added with vigorous agitation a monomer mixture of 260 g butyl acrylate, 230 g methyl methacrylate and 10 g methacrylic acid and stirred for 10 minutes.
  • POLYSTEP ® TSP-16S tristyrylphenol 16 mole ethoxylate sulfate
  • the reaction was maintained at 83 °C for an additional hour, and then cooled with blown air to room temperature.
  • 0.6 g ACTICIDE ® MBS biocide was added.
  • the latex was filtered through a 100 mesh screen, collected 0.15 g coagulum.
  • the final average latex particle size was 250 nm.
  • Latex paints were formulated using pre-dispersed titanium dioxide (Ti0 2 ) from DuPont (Wilmington, Delaware), TI-PURE® R-746 at 76.62% solids. While mixing from an overhead mixer, Dl Water, Propylene Glycol, followed by the addition of MAKON ® TD-9 was added to the pigment. After mixing for about 15 minutes, the sample was poured off into smaller jars in equal amounts. Each aliquot received a latex described above while being stirred by an overhead mixer. The samples were then preserved with ACTICIDE ® MBS.
  • the thickener ACROYSOLTM SCT-275 (a nonionic urethane rheology modifier for latex paints, Dow Chemical, Midland, Michigan) was then slowly added to the paint to increase viscosity. The paints were left to mix for 10 minutes followed by the addition of ammonium hydroxide to increase the pH to 8.5.
  • the coalescing solvent TEXANOLTM ester alcohol (2,2,4-trimethyl-1 ,3-pentanediol monoisobutyrate, Eastman Chemical, Kingsport, Tennessee) was then added to each of the paint formulations. Additional amounts of ACROYSOLTM SCT-275 was added to each paint as required to incrementally increase paint viscosity until the desired viscosity was reached, about 93 KU. The viscosity was allowed to stabilize overnight. The resulting paint formulation yielded 48% solids.
  • Leveling was determined using method ASTM D4062.
  • the paint coatings were drawn down by hand on Black and White Leveling Charts using a leveling blade.
  • the samples were dried for 24 hours at room temperature.
  • the drawn down samples were compared to standards to determine the leveling characteristics.
  • the draw downs produced smooth films free of fisheyes. The results are visually ranked, 9: Good leveling characteristic, 1 : Poor leveling characteristic. See Table 1 below.
  • Blister resistance samples were drawn down using a small minimum form forming temperature bar (MFFT) bar on aged alkyd panels. The panels were left to dry at room temperature for 14 days. Samples were cut into 1 .5" x 1 .5" squares and placed into 4oz jars of 90 °C Dl Water and stored for 7 days. The samples were removed and photographed to compare blister results. The results are visual as described. See Table 1.
  • MFFT small minimum form forming temperature bar
  • Finished latexes were drawn down using a 20 micron wet film applicator onto vinyl chloride/acetate copolymer black scrub test panels (Gardco Form P121 -1 ON plastic panels).
  • the wet films were stored in a 75 °C oven for 30 minutes to dry.
  • the dried films were removed from the oven, cut into 1 .5 in. x 1 .5 in. squares, and the initial opacity on the samples (black) was determined.
  • the films were stored in 4 oz. jars containing 25 °C water and stored 2 hours. After 2 hours the samples were removed from the jars and quickly patted down with KIMWIPES ® to remove excess water.
  • Example 17 Latex Synthesis Using Surfactant (3.0%) from Example 4
  • the ME was prepared by adding 15.2 g of the sulfosuccinate diester as described in example 4 in 147 g Dl water to which was added with vigorous agitation a monomer mixture of 260 g butyl acrylate, 230 g methyl methacrylate and 10 g methacrylic acid and stirred for 10 minutes. Within three minutes after the addition of the ME and ammonium persulfate initiator an exotherm to 85 °C was observed indicating polymerization of the monomers. Dynamic light scattering indicated the in-situ seed average particle size distribution to be 82 nm.
  • the ME was added by metering pump over a three hour period concurrent with the addition of a solution consisting of 2.7 g ammonium persulfate, 1 .5 g sodium bicarbonate dissolved in 75 g Dl water.
  • the reaction temperature was maintained at 83 °C.
  • the ME and initiator feed additions were complete.
  • the ME addition line was flushed with 50 g Dl water into the reactor. The reaction was maintained at 83 °C for an additional hour, and then cooled with blown air to room temperature.
  • the resulting latex was pH adjusted from 5.4 to 7.5 with dilute ammonium hydroxide followed by the addition of 0.6 g ACTICIDE® MBS biocide (1 :1 (by wt.) of 1 ,2-benzisothiazolin-3-one and 2-methyl-4-isothiazolin-3-one, Thor Specialties, Inc., Shelton, Connecticut).
  • the latex was filtered through a 100 mesh screen, 0.21 g of coagulum was collected on the screen.
  • the reactor was clean- free of coagulum, slight coagulum build-up on stirrer blade.
  • the final average latex particle size was 120 nm.
  • the ME was prepared by adding 1 1 .5 g of the B-5 described above to 142 g Dl water to which was added with vigorous agitation a monomer mixture of 260 g butyl acrylate, 230 g methyl methacrylate and 10 g methacrylic acid and stirred for 10 minutes. Within three minutes after the addition of the ME and ammonium persulfate initiator solution an exotherm to 85 °C was observed indicating polymerization of the monomers. Dynamic light scattering indicated the in-situ seed average particle size distribution to be 46 nm.
  • the ME was added by metering pump over a three hour period concurrent with the addition of a solution consisting of 2.7 g ammonium persulfate, 1 .5 g sodium bicarbonate dissolved in 75 g Dl water.
  • the reaction temperature was maintained at 83 °C.
  • the ME and initiator feed additions were complete.
  • the ME addition line was flushed with 50 g Dl water into the reactor. The reaction was maintained at 83 °C for an additional hour, and then cooled with blown air to room temperature.
  • the resulting latex was pH adjusted from 5.5 to 7.5 with 6.6 g of dilute ammonium hydroxide followed by the addition of 0.6 g ACTICIDE® MBS biocide (1 :1 by wt.) of 1 ,2-benzisothiazolin-3-one and 2-methyl-4- isothiazolin-3-one, Thor Specialties, Inc., Shelton, Connecticut).
  • the latex was filtered through a 100 mesh screen; 0.6 g of coagulum was collected on the screen.
  • the reactor was clean- free of coagulum build-up.
  • the final average latex particle size was 1 16 nm.
  • Finished latexes from examples 17 and 18 were drawn down on clear polyester films using a #22 wire wound rod, film A and film B, respectively.
  • the wet films were stored in a 100 °C oven for 3 minutes to dry.
  • the dried films were removed from the oven, stored under ambient conditions for 10 minutes then cut into approximately 2 in. x 2 in. squares.
  • the films were stored in 4 oz. jars containing room temperature Dl water (-23 °C) for about 24 hours.
  • the films were removed from the jars, wiped dry, placed on black plastic panels and photographed.
  • the latex from example 17 (Film A) became somewhat milky losing some clarity whereas the film from example 18 (Film B) became nearly 100% opaque.
  • the ME was added by metering pump over a three hour period concurrent with the addition of a solution consisting of 2.7 g ammonium persulfate, 1 .5 g sodium bicarbonate dissolved in 75 g Dl water.
  • the reaction temperature was maintained at 83 °C.
  • the ME and initiator feed additions were complete.
  • the ME addition line was flushed with 50 g Dl water into the reactor. The reaction was maintained at 83 °C for an additional hour, and then cooled with blown air to room temperature.
  • the resulting latex was pH adjusted from approximately 5.2 to 7.5 with dilute ammonium hydroxide followed by the addition of 0.7 g ACTICIDE ® GA biocide (blend of chlorinated and non-chlorinated isothiazolinones and 2-bromo-2-nitro-1 , 3 propanediol, Thor Specialties, Inc., Shelton, Connecticut).
  • the latex was filtered through a 100 mesh screen.
  • Latex examples 20 (45.8% solids), 21 (45.8% solids), 22 (45.5% solids), 23(45.6% solids), 24(46% solids), and 25(45.8% solids) were applied to corona treated polyester films and surface wetting properties were noted. All latexes required an additional wetting agent to create a uniform continuous polymer film. 15.0 grams of latex was added to a scintillation vial along with dioctyl sulfosuccinate (Aerosol OT-75, 75% solids, Cytec industries, New Jersey) followed by mixing using a vortex mixer. The level to achieve complete surface wetting was noted. Results appear in tables 4 to 9. Table 4 (Example 20)
  • Examples 21 to 25 require 3.3, 2.2, 3.3, 0.0, and 2.2% less surfactant, respectively to wet the polyester surface and produce a continuous uniform film compared to Example 20.
  • Example 27 Water Sensitivity Test of PSA Latex Films on Polyester Film
  • latex films made from latex emulsions comprising surfactants in accordance with the present technology had less opacity (better optical clarity) than the latex film made from a latex emulsion comprising a prior art surfactant.

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Abstract

La présente invention concerne l'utilisation de nouveaux tensioactifs dans la synthèse de latex polymères en émulsion, en particulier ceux utilisés dans les peintures, les revêtements et les auto-adhésifs. Les compositions tensioactives pour les latex polymères en émulsion comprennent des tensioactifs stériquement encombrés dont la composition comprend au moins un sulfosuccinate aromatique substitué par polyaryle alkoxylé. Les nouveaux tensioactifs permettent la production de latex polymères en émulsion stable à distribution granulométrique faible. Les latex ainsi obtenus, lorsqu'ils sont formulés dans des peintures au latex, confèrent des améliorations en termes de résistance à l'eau telle que mesurée par opacité de film, de résistance au cloquage et de caractéristiques d'étalement, et lorsqu'ils sont formulés dans des auto-adhésifs, confèrent de meilleures caractéristiques de résistance à l'eau telle que mesurée par opacité de film.
PCT/US2015/015115 2014-02-12 2015-02-10 Sulfosuccinates d'alkoxylate de tristyrylphénol WO2015123162A1 (fr)

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MX2016010143A MX2016010143A (es) 2014-02-12 2015-02-10 Sulfosuccinatos de triestirilfenol alcoxilatos.
BR112016018484-0A BR112016018484B1 (pt) 2014-02-12 2015-02-10 Emulsão compreendendo triestirilfenol alcoxilato sulfossuccinatos, processo para a preparação de um látex de polímero em emulsão, tinta látex e látex de polímero em emulsão
CN201580008582.0A CN105980465B (zh) 2014-02-12 2015-02-10 三苯乙烯基苯酚烷氧基化磺基琥珀酸酯
EP15748591.3A EP3105285B1 (fr) 2014-02-12 2015-02-10 Sulfosuccinates d'alkoxylate de tristyrylphénol
US15/228,783 US10040964B2 (en) 2014-02-12 2016-08-04 Use of tristyrylphenol alkoxylate sulfosuccinates in emulsion polymerization and coatings
US16/026,564 US20180312712A1 (en) 2014-02-12 2018-07-03 The Use of Tristyrylphenol Alkoxylate Sulfosuccinates in Emulsion Polymerization and Coatings

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KR102384394B1 (ko) 2018-12-13 2022-04-07 주식회사 엘지화학 딥 성형용 라텍스 조성물, 이의 제조방법 및 이로부터 성형된 성형품
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US20160340526A1 (en) 2016-11-24
MX2016010143A (es) 2016-11-15
EP3105285B1 (fr) 2018-12-12
CN105980465A (zh) 2016-09-28
US10040964B2 (en) 2018-08-07
CN105980465B (zh) 2018-09-18
EP3105285A4 (fr) 2017-10-04
US20180312712A1 (en) 2018-11-01
BR112016018484B1 (pt) 2021-09-28
BR112016018484A2 (pt) 2018-07-10
EP3105285A1 (fr) 2016-12-21

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